CN113937272B - Titanium dioxide nano composite material, preparation method and application - Google Patents
Titanium dioxide nano composite material, preparation method and application Download PDFInfo
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- CN113937272B CN113937272B CN202111201891.3A CN202111201891A CN113937272B CN 113937272 B CN113937272 B CN 113937272B CN 202111201891 A CN202111201891 A CN 202111201891A CN 113937272 B CN113937272 B CN 113937272B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a titanium dioxide nano composite material, a preparation method and application, and belongs to the technical field of composite material preparation. Dropwise adding NaOH solution into ruthenium chloride hydrate solution, continuously stirring, adjusting the pH value to be neutral, washing with NaCl solution, and drying to obtain ruthenium dioxide hydrate powder; mixing the hydrated ruthenium dioxide powder with active carbon, and adding a binder to obtain a ruthenium oxide-active carbon composite material; dispersing the ruthenium oxide-activated carbon composite material in an alcohol solution, adding a titanium source in batches, and performing ultrasonic dispersion and calcination treatment to obtain the titanium dioxide nano composite material. The titanium dioxide nano composite material provided by the invention has excellent electrochemical performance, and a lithium ion battery manufactured by using the titanium dioxide nano composite material has excellent cycle stability and rate capability, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of composite material preparation, in particular to a titanium dioxide nano composite material, a preparation method and application.
Background
Titanium dioxide has the characteristics of high catalytic activity, large specific surface area, good light absorptivity, good dispersibility, nontoxicity, high chemical stability and the like, and is widely used as a photoelectric catalyst in the fields of photocatalysis and photodegradation of toxic substances such as organic dyes and the like, construction of biosensors, preparation of new energy materials and the like. However, the titanium dioxide has relatively poor conductivity, which limits the application of the titanium dioxide in the field of battery preparation. Patent No. CN109671920A discloses a composite electrode material of nano-diamond and a titanium dioxide hollow sphere, wherein the titanium dioxide is in a hollow sphere state, nano-diamond particles are in a granular state and are adsorbed on the surface of the titanium dioxide hollow sphere, the preparation method comprises the steps of nano-diamond treatment, strong alkaline solution preparation, sealing reaction in an autoclave, calcination and the like, the prepared product has small grain size and good crystallinity, but the cycling stability and the rate capability of a battery prepared from the composite electrode material are required to be further improved.
Disclosure of Invention
The invention aims to provide a titanium dioxide nano composite material, a preparation method and application, and aims to solve the problem that the cycling stability and the rate capability of a battery in the prior art need to be improved.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a titanium dioxide nano composite material, which comprises the following steps:
(1) Dropwise adding NaOH solution into the ruthenium chloride hydrate solution, continuously stirring, adjusting the pH value to be neutral, washing with NaCl solution, and drying to obtain ruthenium dioxide hydrate powder;
(2) Mixing the hydrated ruthenium dioxide powder with activated carbon, and adding a binder to obtain a ruthenium oxide-activated carbon composite material;
(3) Dispersing the ruthenium oxide-activated carbon composite material in an alcohol solution, adding a titanium source in batches, and performing ultrasonic dispersion and calcination treatment to obtain the titanium dioxide nano composite material.
Further, the concentration of the ruthenium chloride hydrate solution in the step (1) is 0.3-0.5 mol/L, the concentration of the NaOH solution is 0.4-0.6 mol/L, and the concentration of the NaCl solution is 0.5-0.8 mol/L; the volume ratio of the ruthenium chloride hydrate solution to the NaCl solution is (5-6) to (1-3).
Furthermore, the mass ratio of the hydrated ruthenium dioxide powder, the activated carbon and the binder in the step (2) is (5-8) to (3-5) to (1-2).
Further, in the step (2), the binder is any one of polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethyl cellulose.
Further, the alcoholic solution in the step (3) is absolute ethyl alcohol, and the titanium source is any one of titanium isopropoxide, titanium sulfate, titanyl sulfate and titanyl difluoride.
Further, the mass volume ratio of the ruthenium oxide-activated carbon composite material, the alcoholic solution and the titanium source in the step (3) is (5-6) g, (20-30) mL and (4-8) g; the titanium source is added in two times, wherein the first time is added with 1/4 of the total mass of the titanium source, the stirring is carried out for 10-15 min, and the second time is added with the rest titanium source, and the stirring is carried out for 15-20 min.
Further, the time of ultrasonic dispersion in the step (3) is 1-1.5 h, the temperature of the calcination is raised to 800-850 ℃ at the temperature rise rate of 5-10 ℃/min, and the temperature is kept for 10-20 min.
The invention provides a titanium dioxide nano composite material prepared by the preparation method of the titanium dioxide nano composite material.
The invention also provides an application of the titanium dioxide nano composite material in the preparation of a lithium ion battery.
The invention has the following technical effects:
according to the invention, hydrated ruthenium dioxide powder is combined with activated carbon by using a binder, and then a titanium source is added to obtain the titanium dioxide nano composite material through ultrasonic dispersion and calcination. The proportion of the ruthenium dioxide and the active carbon influences the property of the composite material, the chemical reaction is not easy to occur due to the overhigh content of the active carbon, the capacitance characteristic of the electrode material is reduced, the impedance characteristic of the electrode material is influenced due to the overhigh content of the ruthenium dioxide, the capacitance characteristic and the impedance characteristic are in the optimal state by strictly controlling the proportion of the ruthenium dioxide and the active carbon, and the requirement of the quick charging and discharging performance of the battery can be met. The ruthenium oxide-activated carbon composite material is combined with the titanium source, and the titanium source is added in batches, so that the full reaction among all substances is facilitated, the defect of poor conductivity of titanium dioxide is overcome, and the lithium ion battery prepared from the composite material has excellent cycle stability and rate capability and good application prospect.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the documents are cited. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
(1) Dropwise adding NaOH solution (0.5 mol/L) into 25mL of hydrated ruthenium chloride solution (0.4 mol/L), continuously stirring, adjusting the pH value to 7, washing for 1 time by using 10mL of NaCl solution (0.6 mol/L), and drying to obtain hydrated ruthenium dioxide powder;
(2) Mixing the hydrated ruthenium dioxide powder with activated carbon, adding polyvinyl alcohol, and uniformly mixing, wherein the mass ratio of the hydrated ruthenium dioxide powder to the activated carbon to the polyvinyl alcohol is 6;
(3) Dispersing a ruthenium oxide-activated carbon composite material in absolute ethyl alcohol, adding titanium sulfate in batches, wherein the mass-volume ratio of the ruthenium oxide-activated carbon composite material to the absolute ethyl alcohol to the titanium sulfate is 5.5g.
Example 2
(1) Dropwise adding NaOH solution (0.4 mol/L) into 30mL of ruthenium chloride hydrate solution (0.3 mol/L), continuously stirring, adjusting the pH value to 7, washing for 1 time by using 5mL of NaCl solution (0.5 mol/L), and drying to obtain ruthenium dioxide hydrate powder;
(2) Mixing the hydrated ruthenium dioxide powder with active carbon, adding polytetrafluoroethylene, and uniformly mixing, wherein the mass ratio of the hydrated ruthenium dioxide powder to the active carbon to the polytetrafluoroethylene is (5);
(3) Dispersing a ruthenium oxide-activated carbon composite material in absolute ethyl alcohol, adding titanium isopropoxide in batches, wherein the mass-volume ratio of the ruthenium oxide-activated carbon composite material to the absolute ethyl alcohol to the titanium isopropoxide is 5 g.
Example 3
(1) Dropwise adding NaOH solution (0.6 mol/L) into 25mL of hydrated ruthenium chloride solution (0.5 mol/L), continuously stirring, adjusting the pH value to 7, washing for 2 times by using 15mL of NaCl solution (0.8 mol/L), and drying to obtain hydrated ruthenium dioxide powder;
(2) Mixing the hydrated ruthenium dioxide powder with active carbon, and then adding sodium carboxymethylcellulose, wherein the mass ratio of the hydrated ruthenium dioxide powder to the active carbon to the sodium carboxymethylcellulose is (8);
(3) Dispersing a ruthenium oxide-activated carbon composite material in absolute ethyl alcohol, adding difluorooxytitanium in batches, wherein the mass-volume ratio of the ruthenium oxide-activated carbon composite material to the absolute ethyl alcohol to the difluorooxytitanium is 6g, 8g, 1/4 of the total mass of the difluorooxytitanium is added for the first time, stirring is carried out for 12min, the rest difluorooxytitanium is added for the second time, stirring is carried out for 18min, ultrasonic dispersion is carried out for 1.5h, calcination treatment is carried out, the temperature is increased to 850 ℃ at the heating rate of 10 ℃/min, and heat preservation is carried out for 10min, so that the titanium dioxide nanocomposite is obtained.
Comparative example 1
The same as in example 1 except that an NaOH solution (0.5 mol/L) was added dropwise to 50mL of a ruthenium chloride hydrate solution (0.4 mol/L) to adjust the pH to 6.
Comparative example 2
The same as example 1 except that the mass ratio of the hydrated ruthenium dioxide powder, the activated carbon and the polyvinyl alcohol was 3.
Comparative example 3
The same as example 1, except that the mass volume ratio of the ruthenium oxide-activated carbon composite material to the anhydrous ethanol to the titanium sulfate was 8g.
Comparative example 4
The difference from example 1 is that in step (3), the temperature is raised to 600 ℃ at a rate of 5 ℃/min and maintained for 15min.
Comparative example 5
The difference from example 1 is that no hydrated ruthenium dioxide powder is added.
Comparative example 6
The difference from example 1 is that no activated carbon is added.
Comparative example 7
The procedure is as in example 1 except that the titanium source is added in one portion and stirred for 10min after the addition.
Test example 1
80wt% of titanium dioxide nanocomposite (examples 1-3 and comparative examples 1-7), 10wt% of polyvinylidene fluoride and 10wt% of carbon black are mixed and ground, 10 drops of NMP are added and uniformly stirred, the mixed sticky matter is coated on a copper sheet and is placed in a vacuum drying oven to be dried for 6 hours at 100 ℃ to obtain a lithium ion battery cathode, and the performance of the lithium ion battery (CR-2025 type button battery) using the lithium ion battery cathode is tested, wherein the multiplying power is 0.5C, and the voltage range is 1-2.5V, and the results are shown in Table 1.
TABLE 1
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (8)
1. The preparation method of the titanium dioxide nano composite material is characterized by comprising the following steps:
(1) Dropwise adding NaOH solution into the ruthenium chloride hydrate solution, continuously stirring, adjusting the pH value to be neutral, washing with NaCl solution, and drying to obtain ruthenium dioxide hydrate powder;
(2) Mixing the hydrated ruthenium dioxide powder with activated carbon, and adding a binder to obtain a ruthenium oxide-activated carbon composite material;
(3) Dispersing the ruthenium oxide-activated carbon composite material in an alcohol solution, adding a titanium source in batches, and performing ultrasonic dispersion and calcination treatment to obtain a titanium dioxide nano composite material;
in the step (2), the mass ratio of the hydrated ruthenium dioxide powder to the activated carbon to the binder is (5-8) to (3-5) to (1-2);
the mass volume ratio of the ruthenium oxide-active carbon composite material, the alcoholic solution and the titanium source in the step (3) is (5-6) g, (20-30) mL and (4-8) g;
in the step (3), the temperature of the calcination is increased to 800-850 ℃ at the temperature increasing rate of 5-10 ℃/min, and the temperature is kept for 10-20 min.
2. The method for preparing titanium dioxide nanocomposite as claimed in claim 1, wherein the concentration of the ruthenium chloride hydrate solution in step (1) is 0.3 to 0.5mol/L, the concentration of the NaOH solution is 0.4 to 0.6mol/L, and the concentration of the NaCl solution is 0.5 to 0.8mol/L; the volume ratio of the ruthenium chloride hydrate solution to the NaCl solution is (5-6) to (1-3).
3. The method for preparing the titanium dioxide nanocomposite material as claimed in claim 1, wherein the binder in the step (2) is any one of polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
4. The method for preparing the titanium dioxide nanocomposite material as claimed in claim 1, wherein the alcoholic solution in step (3) is absolute ethanol, and the titanium source is any one of titanium isopropoxide, titanium sulfate, titanyl sulfate and titanyl difluoride.
5. The method for preparing the titanium dioxide nano composite material according to the claim 1, wherein the titanium source is added in the step (3) in two times, the first time is 1/4 of the total mass of the titanium source, the stirring is carried out for 10-15 min, and the rest titanium source is added in the second time and the stirring is carried out for 15-20 min.
6. The method for preparing titanium dioxide nano composite material according to claim 1, wherein the time of ultrasonic dispersion in the step (3) is 1-1.5 h.
7. A titanium dioxide nanocomposite material produced by the method for producing a titanium dioxide nanocomposite material according to any one of claims 1 to 6.
8. Use of the titanium dioxide nanocomposite material according to claim 7 in the preparation of lithium ion batteries.
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